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==== Fish and aquatic life====
==== Fish and aquatic life====

Glyphosate is generally less persistent in water than in soil, with 12 to 60-day persistence observed in Canadian ponds, yet persistence of over a year has been recorded in the sediments of U.S. ponds.<ref name="epa_reds"/> The half-life of glyphosate in water is between 12 days to 10 weeks.<ref name="Sparling">{{cite journal|author=Sparling, D.W., Matson, C., Bickham, J. and Doelling‐Brown, P.|year=2006|title=Toxicity of glyphosate as Glypro® and LI700 to red‐eared slider (Trachemys scripta elegans) embryos and early hatchlings|journal=Environmental Toxicology and Chemistry|volume=25|issue=10|pages=2768–2774}}</ref>
A 2005 study stated that measures of aquatic glyphosate prevalence (frequency of glyphosate and AMPA detection, range of concentrations in runoff samples, and ratios of AMPA to glyphosate concentrations) did not vary throughout the growing season as substantially as for other herbicides like atrazine. It was suggested this was probably because of different seasonal use patterns.<ref name="Battaglin">{{cite journal|Battaglin, W.A., Kolpin, D.W., Scribner, E.A., Kuivila, K.M. and Sandstrom, M.W.|year=2005|title=Glyphosate, other herbicides, and transformation products in midwestern streams|journal=Journal of the American Water Resources Association.|volume=41|issue=2|pages=323–332}}</ref> Glyphosate is generally less persistent in water than in soil, with 12 to 60-day persistence observed in Canadian ponds, yet persistence of over a year has been recorded in the sediments of U.S. ponds.<ref name="epa_reds"/> The half-life of glyphosate in water is between 12 days to 10 weeks.<ref name="Sparling">{{cite journal|author=Sparling, D.W., Matson, C., Bickham, J. and Doelling‐Brown, P.|year=2006|title=Toxicity of glyphosate as Glypro® and LI700 to red‐eared slider (Trachemys scripta elegans) embryos and early hatchlings|journal=Environmental Toxicology and Chemistry|volume=25|issue=10|pages=2768–2774}}</ref>


In various freshwater fish species, pure glyphosate has a 48-hour lethal concentration (LC<sub>50</sub>) of greater than 24&nbsp;mg/L to 140&nbsp;mg/L, while marketed glyphosate formulations can range from 1.3&nbsp;mg/L to greater than 1000&nbsp;mg/L. Specific species LC<sub>50s</sub> include 140&nbsp;mg/L for [[rainbow trout]] (''Onchorynchus mykiss''), 97&nbsp;mg/L for [[fathead minnow]]s (''Pimephales promelas''), 130&nbsp;mg/L for [[channel catfish]] (''Icalurus punctatus'') and 150&nbsp;mg/L for [[bluegill sunfish]] (''Lepomis macrochirus''). A positive association between exposure to glyphosate and immunotoxicity in fish has been reported and other studies have consistently shown that glyphosate can cause [[oxidative stress]] in fish.<ref>{{cite web|url=http://monographs.iarc.fr/ENG/Monographs/vol112/mono112-02.pdf|title=IARC monograph on glyphosate|publisher=IARC|accessdate=September 27, 2015}}</ref>
In various freshwater fish species, pure glyphosate has a 48-hour lethal concentration (LC<sub>50</sub>) of greater than 24&nbsp;mg/L to 140&nbsp;mg/L, while marketed glyphosate formulations can range from 1.3&nbsp;mg/L to greater than 1000&nbsp;mg/L. Specific species LC<sub>50s</sub> include 140&nbsp;mg/L for [[rainbow trout]] (''Onchorynchus mykiss''), 97&nbsp;mg/L for [[fathead minnow]]s (''Pimephales promelas''), 130&nbsp;mg/L for [[channel catfish]] (''Icalurus punctatus'') and 150&nbsp;mg/L for [[bluegill sunfish]] (''Lepomis macrochirus''). A positive association between exposure to glyphosate and immunotoxicity in fish has been reported and other studies have consistently shown that glyphosate can cause [[oxidative stress]] in fish.<ref>{{cite web|url=http://monographs.iarc.fr/ENG/Monographs/vol112/mono112-02.pdf|title=IARC monograph on glyphosate|publisher=IARC|accessdate=September 27, 2015}}</ref>

Revision as of 17:55, 5 October 2015

Not to be confused with glufosinate.
Glyphosate
Names
IUPAC name
N-(phosphonomethyl)glycine
Other names
2-[(phosphonomethyl)amino]acetic acid
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard 100.012.726 Edit this at Wikidata
EC Number
  • 213-997-4
KEGG
RTECS number
  • MC1075000
UNII
  • InChI=1S/C3H8NO5P/c5-3(6)1-4-2-10(7,8)9/h4H,1-2H2,(H,5,6)(H2,7,8,9) checkY
    Key: XDDAORKBJWWYJS-UHFFFAOYSA-N checkY
  • InChI=1/C3H8NO5P/c5-3(6)1-4-2-10(7,8)9/h4H,1-2H2,(H,5,6)(H2,7,8,9)
    Key: XDDAORKBJWWYJS-UHFFFAOYAE
  • O=C(O)CNCP(=O)(O)O
Properties
C3H8NO5P
Molar mass 169.073 g·mol−1
Appearance white crystalline powder
Density 1.704 (20 °C)
Melting point 184.5 °C (364.1 °F; 457.6 K)
Boiling point decomposes at 187 °C (369 °F; 460 K)
1.01 g/100 mL (20 °C)
log P −2.8
Acidity (pKa) <2, 2.6, 5.6, 10.6
Hazards
GHS labelling:
Eye Dam. 1Aquatic Chronic 2
Danger
H318, H411
P273, P280, P305+P351+P338, P310, P501
Flash point Non-flammable
Safety data sheet (SDS) InChem MSDS
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
☒N verify (what is checkY☒N ?)

Glyphosate (N-(phosphonomethyl)glycine) is a broad-spectrum systemic herbicide used to kill weeds, especially annual broadleaf weeds and grasses known to compete with commercial crops grown around the globe. It was discovered to be an herbicide by Monsanto chemist John E. Franz in 1970.[3] Monsanto brought it to market in the 1970s under the trade name Roundup and Monsanto's last commercially relevant United States patent expired in 2000.

Glyphosate was quickly adopted by farmers, even more so when Monsanto introduced glyphosate-resistant crops, enabling farmers to kill weeds without killing their crops. In 2007, glyphosate was the most used herbicide in the United States agricultural sector, with 180 to 185 million pounds (82,000 to 84,000 tonnes) applied, and the second-most used in home and garden market where users applied 5 to 8 million pounds (2,300 to 3,600 tonnes); in addition, industry, commerce, and government applied 13 to 15 million pounds (5,900 to 6,800 tonnes).[4]

With its heavy use in agriculture, weed resistance to glyphosate is a growing problem. While glyphosate and formulations such as Roundup have been approved by regulatory bodies worldwide and are widely used, concerns about their effects on humans and the environment persist.[5]

Glyphosate's mode of action as an herbicide is to inhibit a plant enzyme involved in the synthesis of the aromatic amino acids: tyrosine, tryptophan, and phenylalanine. It is absorbed through foliage, and minimally through roots,[6][7][8] and translocated to growing points. Because of this mode of action, it is only effective on actively growing plants; it is not effective as a pre-emergence herbicide. Some crops have been genetically engineered to be tolerant of glyphosate (i.e., Roundup Ready, also created by Monsanto Company). Such crops allow farmers to use glyphosate as a postemergence herbicide against weeds, but the development of glyphosate resistance in some weed species is emerging as a costly problem. Roundup Ready soybean was the first Roundup Ready crop.

Many regulatory and scholarly reviews have evaluated the relative toxicity of glyphosate as an herbicide. The German Federal Institute for Risk Assessment published a toxicology review in 2013, which found that "the available data is contradictory and far from being convincing" with regard to correlations between exposure to glyphosate formulations and risk of various cancers, including non-Hodgkin lymphoma (NHL).[9] A meta-analysis published in 2014 identified an increased risk of NHL in workers exposed to glyphosate formulations.[10] In March 2015 the World Health Organization's International Agency for Research on Cancer published a summary of its forthcoming monograph on glyphosate, and classified it as "probably carcinogenic in humans" (category 2A) based on epidemiological studies, animal studies, and in vitro studies.[5][11][12]

Discovery

Glyphosate was first synthesized in 1950 by Swiss chemist Henry Martin, who worked for the Swiss company Cilag. The work was never published.[13]: 1  Stauffer Chemical patented the agent as a chemical chelator in 1964 as it binds and removes minerals such as calcium, magnesium, manganese, copper and zinc.[14]

Somewhat later, glyphosate was independently discovered at Monsanto in 1970. Monsanto chemists had synthesized about 100 analogs of aminomethylphosphonic acid as potential water-softening agents. Two were found to have weak herbicidal activity, and John E. Franz, a chemist at Monsanto, was asked to try to make analogs with stronger herbicidal activity. Glyphosate was the third analog he made.[13]: 1–2 [15]

Glyphosate has been called by experts in herbicides "virtually ideal" due to its broad spectrum and low toxicity to animal life compared with other herbicides.[16][17][18][19] Franz received the National Medal of Technology in 1987[20] and the Perkin Medal for Applied Chemistry[21] in 1990 for his discoveries. Franz was inducted into the National Inventor's Hall of Fame in 2007.[22]

Chemistry

Glyphosate synthesis from chloroacetic acid

Glyphosate is an aminophosphonic analogue of the natural amino acid glycine, and the name is a contraction of gly(cine) phos(phon)ate. The molecule has several dissociable hydrogens, especially the first hydrogen of the phosphate group. The molecule tends to exist as a zwitterion where a phosphonic hydrogen dissociates and joins the amine group. Glyphosate is soluble in water to 12 g/L at room temperature.

Glyphosate synthesis from dimethyl phosphite

The main deactivation path is hydrolysis to aminomethylphosphonic acid (AMPA).[23]

Biochemistry

Glyphosate kills plants and many bacteria by interfering with the synthesis of the aromatic amino acids phenylalanine, tyrosine, and tryptophan. It does this by inhibiting the enzyme 5-enolpyruvylshikimate-3-phosphate synthase (EPSPS), which catalyzes the reaction of shikimate-3-phosphate (S3P) and phosphoenolpyruvate to form 5-enolpyruvyl-shikimate-3-phosphate (EPSP).[24]

File:EPSPreactionII.tif

EPSP is subsequently dephosphorylated to chorismate, an essential precursor for the amino acids mentioned above.[25] These amino acids are used in protein synthesis and to produce secondary metabolites such as folates, ubiquinones, and naphthoquinone.

X-ray crystallographic studies of glyphosate and EPSPS show that glyphosate functions by occupying the binding site of the phosphoenolpyruvate, mimicking an intermediate state of the ternary enzyme substrates complex.[26][27] Glyphosate inhibits the EPSPS enzymes of different species of plants and microbes at different rates.[28][29]

EPSPS is produced only by plants and microbes; the gene coding for it is not in the mammalian genome.[30][31] Gut flora of some animals contain EPSPS.[32]

Glyphosate is absorbed through foliage and minimally through roots. Because of this mode of action, it is only effective on actively growing plants; it is not effective in preventing seeds from germinating.[7][8]

Environmental fate

Glyphosate adsorbs strongly to soil, and residues are expected to generally be immobile in soil. Ground and surface water pollution is limited. Glyphosate is readily degraded by soil microbes to aminomethylphosphonic acid (AMPA). Glyphosate and AMPA are not likely to move to ground water due to their strong adsorptive characteristics. Glyphosate does have the potential to contaminate surface waters due to its aquatic use patterns and through erosion, as it adsorbs to soil particles suspended in runoff. Limited leaching can also occur after high rainfall after application. If glyphosate reaches surface water, it is not broken down readily by water or sunlight.[33][34]

The half-life of glyphosate in soil ranges between 2 and 197 days; a typical field half-life of 47 days has been suggested. Soil and climate conditions affect glyphosate's persistence in soil. The median half-life of glyphosate in wate varies from a few to 91 days.[7] At a site in Texas half-live was as little as three days to 141 days at a site in Iowa.[35] The glyphosate metabolite AMPA has been found in Swedish forest soils up to two years after a glyphosate application. In this case, the persistence of AMPA was attributed to the soil being frozen for most of the year.[36] Glyphosate adsorption to soil, and later release from soil, varies depending on the kind of soil.[37][38] A 2009 study using a RoundUp formulation concluded absorption into plants delays subsequent soil degradation and can increase glyphosate persistence in soil from two to six times.[39]

According to the National Pesticide Information Center fact sheet, glyphosate is not included in compounds tested for by the Food and Drug Administration's Pesticide Residue Monitoring Program, nor in the United States Department of Agriculture's Pesticide Data Program. However, a field test showed that lettuce, carrots, and barley contained glyphosate residues up to one year after the soil was treated with 3.71 lb of glyphosate per acre (4.15 kg per hectare).[7]

Use

Glyphosate used as an alternative to mowing in an apple orchard in Ciardes, Italy

Glyphosate is effective in killing a wide variety of plants, including grasses and broadleaf and woody plants. By volume, it is one of the most widely used herbicides.[7] It is commonly used for agriculture, horticulture, viticulture, and silviculture purposes, as well as garden maintenance (including home use).[7][40] It has a relatively small effect on some clover species and morning glory.[41]

In many cities, glyphosate is sprayed along the sidewalks and streets, as well as crevices in between pavement where weeds often grow. However, up to 24% of glyphosate applied to hard surfaces can be run off by water.[42] Glyphosate contamination of surface water is attributed to urban and agricultural use.[43] Glyphosate is used to clear railroad tracks and get rid of unwanted aquatic vegetation.[8] Since 1994, glyphosate has been used in aerial spraying in Colombia in coca eradication programs; Colombia announced in May 2015 that by October it would cease using glyphosate in these programs due to concerns about human toxicity of the chemical.[44]

In addition to its use as an herbicide, glyphosate is also used for crop desiccation (siccation) to increase harvest yield[8] and, as a result of desiccation, to increase sucrose concentration in sugarcane before harvest.[45]

Formulations and tradenames

Glyphosate is marketed in the United States and worldwide by many agrochemical companies, in different solution strengths and with various adjuvants, under dozens of tradenames.[46][47][48][49] As of 2010, there were more than 750 glyophosate products on the market.[50] In 2012, in terms of volume about half of the total global consumption of glyphosate was for conventional crops; Asia Pacific was the largest and fastest growing market.[51] Chinese manufacturers collectively are the world's largest producers of glyphosate and its precursors[52] and account for about 30% of global exports.[51] Key manufacturers include Anhui Huaxing Chemical Industry Compan, BASF, Bayer CropScience, Dow AgroSciences, DuPont, Jiangsu Good Harvest-Weien Agrochemical Company, Monsanto, Nantong Jiangshan Agrochemical & Chemicals Co., Nufarm Limited, SinoHarvest, Syngenta, and Zhejiang Xinan Chemical Industrial Group Company.[51]

Glyphosate is an acid molecule, so it is formulated as a salt for packaging and handling. Various salt formulations include isopropylamine, diammonium, monoammonium, or potassium as the counterion. Some brands include more than one salt. Some companies report their product as acid equivalent (ae) of glyphosate acid, or some report it as active ingredient (ai) of glyphosate plus the salt, and others report both. To compare performance of different formulations, knowledge of how the products were formulated is needed. Since the salt does not contribute to weed control and different salts have different weights, the acid equivalent is a more accurate method of expressing and comparing concentrations.[53] Adjuvant loading refers to the amount of adjuvant[54][55] already added to the glyphosate product. Fully loaded products contain all the necessary adjuvants, including surfactant; some contain no adjuvant system, while other products contain only a limited amount of adjuvant (minimal or partial loading) and additional surfactants must be added to the spray tank before application.[53] As of 2000 (just before Monsanto's patent on glyphosate expired), over 400 commercial adjuvants from over 34 different companies were available for use in commercial agriculture.[56][57]

Products are supplied most commonly in formulations of 120, 240, 360, 480, and 680 g/l of active ingredient. The most common formulation in agriculture is 360 g/l, either alone or with added cationic surfactants.[47]

For 360 g/l formulations, European regulations allow applications of up to 12 l/ha for control of perennial weeds such as couch grass. More commonly, rates of 3 l/ha are practiced for control of annual weeds between crops.[58]

Monsanto

Monsanto's Roundup is the earliest formulation of glyphosate.

Monsanto developed and patented the use of glyphosate to kill weeds in the 1970s, and has marketed it as Roundup since 1973. It retained exclusive rights in the United States until its patent expired in September, 2000.

As of 2009, sales of these herbicide products represented about 10% of Monsanto's revenue due to competition from other producers of other glyphosate-based herbicides;[59] their Roundup products (which include GM seeds) represented about half of Monsanto's gross margin.[60]

The active ingredient of the Monsanto herbicides is the isopropylamine salt of glyphosate. Another important ingredient in some formulations is the surfactant polyethoxylated tallow amine.

Monsanto also produces seeds which grow into plants genetically engineered to be tolerant to glyphosate. The genes contained in these seeds are patented. Such crops allow farmers to use glyphosate as a postemergence herbicide against most broadleaf and cereal weeds. Soy was the first glyphosate-resistant crop.

Toxicity

Glyphosate is the active ingredient in herbicide formulations containing it. However, in addition to glyphosate salts, commercial formulations of glyphosate contain additives such as surfactants which vary in nature and concentration. Toxicologists have studied glyphosate alone, additives alone, and formulations. Although surfactants probably contribute to the acute toxicity of glyphosate formulations, the weight of evidence is against surfactants potentiating the toxicity of glyphosate.[61] The source says:

Although surfactants probably contribute to the acute toxicity of glyphosate formulations, the weight of evidence is against surfactants potentiating the toxicity of glyphosate.

Active ingredient

Mammals

The LD50 of glyphosate is 5,000 mg/kg for rats, 10,000 mg/kg in mice and 3,530 mg/kg in goats. The acute dermal LD50 in rabbits is greater than 2 g/kg. Mammalian LD50s are considered to be low to very low toxicity. Signs of glyphosate toxicity in animals typically appear within 30 minutes to 2 hours following ingestion of a large enough dose, and include initial excitability and tachycardia, ataxia, depression and bradycardia but severe cases can develop into collapse and convulsions.[7]

A review of unpublished short-term rabbit feeding studies reported severe toxicity effects at 150 mg/kg/day and "no observed adverse effect level" (NOAEL) doses ranging from 50 to 200 mg/kg/day.[62]

Glyphosate can have carcinogenic effects in non-human mammals. These include the induction of positive trends in the incidence of renal tubule carcinoma and haemangiosarcoma in male mice, and increased pancreatic islet-cell adenoma in male rats.[11] A 2015 review found that glyphosate may be toxic below the lowest-observed-adverse-effect level that has been assigned to it by regulators, and that its effects may include "teratogenic, tumorigenic and hepatorenal effects."[63]

Humans

Human acute toxicity is dose-related. Acute fatal toxicity has been reported in deliberate overdose.[61][64] Early epidemiological studies did not find associations between long-term low-level exposure to glyphosate and any disease.[65][66][67] In 2013 the European commission reviewed a 2002 finding that had concluded equivocal evidence existed of a relationship between glyphosate exposure during pregnancy and cardiovascular malformations and found that "there is no increased risk at the levels of exposure below those that caused maternal toxicity."[68] A 2013 review found that neither glyphosate nor typical glyphosate-based formulations (GBFs) pose a genotoxicity risk in humans under normal conditions of human or environmental exposures.[69] A 2000 review concluded that "under present and expected conditions of new use, there is no potential for Roundup herbicide to pose a health risk to humans".[70] A 2002 review by the European Union reached the same conclusion.[71] A 2014 review article reported a significant association between B-cell lymphoma and glyphosate exposure.[10]

Fish and aquatic life

A 2005 study stated that measures of aquatic glyphosate prevalence (frequency of glyphosate and AMPA detection, range of concentrations in runoff samples, and ratios of AMPA to glyphosate concentrations) did not vary throughout the growing season as substantially as for other herbicides like atrazine. It was suggested this was probably because of different seasonal use patterns.[72] Glyphosate is generally less persistent in water than in soil, with 12 to 60-day persistence observed in Canadian ponds, yet persistence of over a year has been recorded in the sediments of U.S. ponds.[33] The half-life of glyphosate in water is between 12 days to 10 weeks.[73]

In various freshwater fish species, pure glyphosate has a 48-hour lethal concentration (LC50) of greater than 24 mg/L to 140 mg/L, while marketed glyphosate formulations can range from 1.3 mg/L to greater than 1000 mg/L. Specific species LC50s include 140 mg/L for rainbow trout (Onchorynchus mykiss), 97 mg/L for fathead minnows (Pimephales promelas), 130 mg/L for channel catfish (Icalurus punctatus) and 150 mg/L for bluegill sunfish (Lepomis macrochirus). A positive association between exposure to glyphosate and immunotoxicity in fish has been reported and other studies have consistently shown that glyphosate can cause oxidative stress in fish.[74]

For green frogs (Rana clamitans) glyphosate has a 24 and 96-hour LC50 of greater than 38.9 g/L. A 2014 review found that amphibians have been identified as particularly sensitive to glyphosate formulations in their larval and tadpole stages of development, and toxicity has been extensively studied for those stages; toxicity for terrestrial life cycle stages is less well understood. The review found that "across the spectrum of organisms likely to be exposed to glyphosate in the aquatic environment, it has been shown that sensitivity to glyphosate (and the constituents of commercial formulas) is highly species-specific. A 2012 study on the toxic potential of environmentally relevant concentrations of glyphosate on wood frogs (Rana sylvatica), leopard frogs (Rana pipiens pipiens) and American toads (Bufo americanus) reported a significant induction of morphological changes in the tadpoles of the three species, including alteration of the size of the tadpole tail. This indicates that the herbicide could be affecting the mechanisms of development that are normally used as defence responses against predators. These results showed that glyphosate "can have widespread and relevant effects on non target species."[75] Developmental toxicity appears to occur in the larval and tadpoles of the American toad at levels of exposure to glyphosate that occur in common use of the herbicide.

In freshwater invertebrates (species unspecified), glyphosate has a 48-hour LC50 ranging from 55 to 780 ppm. The 96-hour LC50 is 281 ppm for grass shrimps (Palaemonetas vulgaris) and 934 ppm for fiddler crabs (Uca pagilator). These values make glyphosate "slightly toxic to practically non-toxic".[7]

A study observing the impact of herbicides on the biodiversity of aquatic communities containing algae and more than 25 species of animals showed that in contrast to 2,4-D, glyphosate had great impact in the community, causing a decrease of 22% of the species richness.[75]

Antimicrobial activity

The antimicrobial activity of glyphosate has been described in the microbiology literature since its discovery in 1970 and the description of glyphosate's mechanism of action in 1972. Efficacy was described for numerous bacterial and fungi.[76] Glyphosate can control the growth of apicomplexan parasites, such as Toxoplasma gondii, Plasmodium falciparum and Cryptosporidium parvum, and has been considered as an antimicrobial agent in mammals. [77] Inhibition can occur with some Rhizobium species important for soybean nitrogen fixation, especially under moisture stress. [78]

Soil biota

Degradation pathway of glyphosate in the ground[79]

When glyphosate comes into contact with the soil, it can be bound to soil particles, thereby slowing its degradation.[33][35] Farmers have noticed changes in soil texture, more compaction, less root nodules in corn.[80] In sewage sludge, unbound glyphosate has been degraded by bacteria.[81][relevant?] Glyphosate and its degradation product, AMPA, residues are considered to be much more toxicologically and environmentally benign than most of the herbicides replaced by glyphosate.[82][relevant?]

Glyphosate can harm the bacterial ecology of soil and cause micronutrient deficiencies in plants.[83] Other studies found that while "recommended dosages of glyphosate did not affect growth rates", much higher dosages reduced respiration in nitrogen-fixing bacteria.[84][85]

The burrowing earthworm, Lumbricus terrestris, stop their activity after 3 weeks of exposure to glyphosate.[clarification needed] Reproduction of two earthworm species was reduced by 56% within three months after glyphosate. This led to increased nitrate soil concentrations by 1,592% and phosphate by 127%, for nutrient leaching into water.[86] Laboratory studies published in 1991 and 1992 indicated GBFs could harm beneficial insects[87] and earthworms.[88] The findings of negative effects of glyphosate on earthworms has been cricized[79] and conflicts with results from 1989 field studies where no effects were noted for a number of nematodes, mites, or [[springtail]s after treatment with Roundup at 2 kg/ha of active ingredient.[89] Monsanto's education sheet on soil microbes from 2011 argues that abundant tests have been done to satisfy regulators, that laboratory based tests are inferior to field tests and focuses on an "undisturbed" Rhizobium relationship.[90]

Genetic damage

Glyphosate produces DNA strand breaks in the comet assay in sábalo, European eel, zebrafish, Nile tilapia.[91]

Government and organization positions on glyphosate toxicity

European Food Safety Authority position

A 2013 systematic review by the German Institute for Risk Assessment (BfR), conducted as part of the EFSA's review process, examined epidemiological studies, animal studies, and in vitro studies that it found valid, and found that "no classification and labelling for carcinogenicity is warranted" and did not recommend a carcinogen classification of either 1A or 1B.[9]: Volume 1, p139, see also 34–37  It was provided to the EFSA in January 2014 and published by the EFSA in December 2014[9][92][93]

US Environmental Protection Agency position

The EPA, which last reviewed glyphosate in 1993, considers glyphosate to be noncarcinogenic and relatively low in dermal and oral acute toxicity.[33] The EPA considered a "worst case" dietary risk model of an individual eating a lifetime of food derived entirely from glyphosate-sprayed fields with residues at their maximum levels. This model indicated that no adverse health effects would be expected under such conditions.[33] As of March 2015, the EPA was in the midst of reviewing glyphosate's toxicity.[5]

World Health Organization position

In March 2015, the International Agency for Research on Cancer published a summary of their forthcoming monograph on glyphosate, and classified glyphosate as "probably carcinogenic in humans" (category 2A) based on epidemiological studies, animal studies, and in vitro studies; it noted that there was "limited evidence" of carcinogenicity in humans for non-Hodgkin lymphoma.[5][11][12][94] The German Institute for Risk Assessment responded that the work group reviewed only a selection of what they had reviewed earlier, and argued that other studies, among them the widely-cited cohort study Agricultural Health Study, do not support the classification.[95] The IARC report did not include the German regulatory study published in December 2014, nor did it include industry-funded studies. The IARC also does not conduct risk assessment; their goal is to classify carcinogenic potential, and "a few positive findings can be enough to declare a hazard, even if there are negative studies as well."[96]

Additive toxicity

Glyphosate formulations may contain a number of adjuvants, the identity of which is considered a trade secret and not disclosed by government regulators. In the United States, the Federal Insecticide, Fungicide, and Rodenticide Act requires that all pesticides (including herbicides) be evaluated by the EPA prior to sale, including product’s chemistry, environmental fate, residue chemistry, dietary and nondietary hazards to humans, and hazards to domestic animals and nontarget organisms[97] These evaluations are performed for each active ingredient, each inert ingredient, and for the final product formulation. Additional evaluations are performed by the FDA to set permitted residue levels in food for pesticide products used on food crops.[98]

Surfactants

Surfactants are used in herbicide formulations as wetting agents, to maximize coverage and aid penetration of the herbicide(s) through plant leaves. As agricultural spray adjuvants, surfactants may be premixed in commercial formulations, such as Roundup, or they may be purchased separately and mixed on-site (tank mix).

Polyethoxylated tallow amine (POEA) is a surfactant used in the original Roundup formulation and is still commonly used today.[99] Different versions of Roundup have included different percentages of POEA. Although Monsanto product fact sheets do not disclose surfactants and their percentages, a 1997 US government report said that Roundup is 15% POEA while Roundup Pro is 14.5%.[100]

A review of the literature provided to the EPA in 1997 found that POEA was more toxic to fish than glyphosate was.[100]

Spreader 90 is a surfactant used in tank mixes.[104] Spreader 90 contains 1,2 propanediol (also known as propylene glycol), propane 1,2,3 triol (also known as glycerol), alcohol ethoxylate, and dimethylpolysiloxane.[105][106] Of these ingredients, alcohol ethoxylates are among the widely used detergents in consumer products; commercial preparations are often mixes of homologs. Due to known toxicities to aquatic species, the Canadian Environmental Protection Act, 1999 recommended Federal Water Quality Guideline values of 70 µg/l.[107]

Inert ingredient toxicity

Glyphosate-based formulations (GBFs) may contain a number of adjuvants, the identities of which are considered trade secret[108] and not disclosed by most government regulators. In the United States, the Federal Insecticide, Fungicide, and Rodenticide Act requires that all pesticides (including herbicides) be evaluated by the EPA prior to sale, including the product’s chemistry, environmental fate, residue chemistry, dietary and non-dietary hazards to humans, and hazards to domestic animals and non-target organisms.[97] These evaluations are performed for each active ingredient, each inert ingredient, and for the final product formulation. Additional evaluations are performed by the FDA to set permitted residue levels in food for pesticide products used on food crops.[98]

Surfactants are used in herbicide formulations as wetting agents and penetrants to maximize coverage and aid penetration of the herbicide(s) through plant leaves. As agricultural spray adjuvants, surfactants may be premixed in commercial formulations or they may be purchased separately and mixed on-site (tank mix).

Polyethoxylated tallow amine (POEA) is a surfactant used in the original Roundup formulation and is still commonly used today.[99] Different versions of Roundup have included different percentages of POEA. Although Monsanto product fact sheets do not disclose surfactants and their percentages, a 1997 US government report said that Roundup is 15% POEA while Roundup Pro is 14.5%.[100] A review of the literature provided to the EPA in 1997 found that POEA was more toxic to fish than glyphosate was.[100]

Spreader 90 is a surfactant used in tank mixes.[109] Spreader 90 contains 1,2 propanediol (also known as propylene glycol), propane 1,2,3 triol (also known as glycerol), alcohol ethoxylate, and dimethylpolysiloxane.[105][106] Of these ingredients, alcohol ethoxylates are among the widely used detergents in consumer products; commercial preparations are often mixes of homologs. Due to known toxicities to aquatic species, the Canadian Environmental Protection Act, 1999 recommended Federal Water Quality Guideline values of 70 µg/l.[107]

Human

A 2000 review concluded that "under present and expected conditions of new use, there is no potential for Roundup herbicide to pose a health risk to humans".[70] A 2002 review by the European Union reached the same conclusion.[71]

Data from the California Environmental Protection Agency's Pesticide Illness Surveillance Program, which also tracks other agricultural chemicals, show glyphosate-related incidents are some of the most common.[110][111] However, incident counts alone do not take into account the number of people exposed and the severity of symptoms associated with each incident.[111] For example, if hospitalization were used as a measure of the severity of incidents, then glyphosate would be considered relatively safe; over a 13-year period in California, none of the 515 reported hospitalizations was attributed to glyphosate.[111]

Dermal exposure to ready-to-use glyphosate formulations can cause irritation, and photocontact dermatitis has been occasionally reported. These effects are probably due to the preservative benzisothiazolin-3-one. Severe skin burns are very rare.[61] Inhalation is a minor route of exposure, but spray mist may cause oral or nasal discomfort, an unpleasant taste in the mouth, or tingling and irritation in the throat. Eye exposure may lead to mild conjunctivitis. Superficial corneal injury is possible if irrigation is delayed or inadequate.[61]

Deliberate ingestion of Roundup in quantities ranging from 85 to 200 ml (of 41% solution) has resulted in death within hours of ingestion, although it has also been ingested in quantities as large as 500 ml with only mild or moderate symptoms.[112] A reasonable correlation is seen between the amount of Roundup ingested and the likelihood of serious systemic sequelae or death. Ingestion of more than 85 ml of the concentrated formulation is likely to cause significant toxicity in adults. Corrosive effects – mouth, throat and epigastric pain and dysphagia – are common. Renal and hepatic impairment are also frequent, and usually reflect reduced organ perfusion. Respiratory distress, impaired consciousness, pulmonary edema, infiltration on chest X-ray, shock, arrhythmias, renal failure requiring haemodialysis, metabolic acidosis, and hyperkalaemia may occur in severe cases. Bradycardia and ventricular arrhythmias often present prior to death.

A 2012 meta-analysis of all epidemiological studies of exposure to glyphosate formulations found no correlation with any kind of cancer.[66] The 2013 systematic review by the German Institute for Risk Assessment of epidemiological studies of workers who use pesticides, exposed to glyphosate formulations found no significant risk, stating that "the available data is contradictory and far from being convincing".[9]: Volume 1, p64-66  However, a 2014 meta-analysis of the same studies found a correlation between occupational exposure to glyphosate formulations and increased risk of B cell lymphoma, the most common kind of non-Hodgkin lymphoma (NHL). Workers exposed to glyphosate were about twice as likely to get B cell lymphoma.[10]

Endocrine disruption

Administering Roundup Transorb orally to prepubescent rats once a day for 30 days reduced testosterone production and affected testicle morphology, but did not affect levels of estradiol and corticosterone.[113]

In 2007, the EPA selected glyphosate for further screening through its Endocrine Disruptor Screening Program (EDSP). Selection for this program is based on a compound's prevalence of use and does not imply particular suspicion of endocrine activity.[114] On June 29, 2015 the EPA released Weight of Evidence Conclusion of the EDSP Tier 1 screening for glyphosate, recommending that glyphosate not be considered for Tier 2 testing. The Weight of Evidence conclusion stated "...there was no convincing evidence of potential interaction with the estrogen, androgen or thyroid pathways."[115]

Genetic damage

Several studies have not found mutagenic effects,[116] so glyphosate has not been listed in the United States Environmental Protection Agency or the International Agency for Research on Cancer databases.[117] Various other studies suggest glyphosate may be mutagenic.[117] Glyphosate-based formulations produce DNA strand breaks in several major taxa of animals including numerous fish species (European eel, sábalo, guppy, bloch, neotropical fish (Corydoras paleatus) carp, goldfish), reptiles (caiman), amphibians (frogs, including tadpoles) and gastropods (snails), but not in oysters, clams and mussel glochidia. In earthworms, one glyphosate-based formulation induced DNA strand breaks while two others did not, thereby emphasising the potential importance of components other than the active ingredients in the formulations.[118]

Other animals

A 2000 review of the ecotoxicological data on Roundup shows at least 58 studies exist on the effects of Roundup on a range of organisms.[79] This review concluded, "...for terrestrial uses of Roundup minimal acute and chronic risk was predicted for potentially exposed non-target organisms".

Fish and aquatic life

Glyphosate formulations are much more toxic for amphibians and fish than glyphosate alone.[100] A 2003 study of various formulations of glyphosate found, "[the] risk assessments based on estimated and measured concentrations of glyphosate that would result from its use for the control of undesirable plants in wetlands and over-water situations showed that the risk to aquatic organisms is negligible or small at application rates less than 4 kg/ha and only slightly greater at application rates of 8 kg/ha.".[119] Serious sub-lethal effects on aquatic animals have been noted for formulations of glyphosate.[73]

The LC50 of formulations for Catla catla is 4.6 ppm,[120] 4.2 ppm for rainbow trout (Oncorhynchus mykiss) and 1.3 ppm for bluegill (Lepomis macrochirus)[121] The 96 h-LC50 toxicity of Roundup for the neotropical fish Prochilodus lineatus is 13.69 mg/L, indicating this fish is more sensitive to Roundup than rainbow trout and Atlantic salmon (Salmo salar).[122] Short-term exposure of Prochilodus lineatus to sub-lethal concentrations of Roundup results in biochemical, physiological and histological alterations. Histopathological changes are observed in the gills, livers and brains in other fishes at these concentrations.[123]

A 2013 meta-analysis reviewed the available data related to potential impacts of glyphosate-based herbicides on amphibians. According to the authors, the use of glyphosate-based pesticides cannot be considered the major cause of amphibian decline, the bulk of which occurred prior to the widespread use of glyphosate or in pristine tropical areas with minimal glyphosate exposure. The authors recommended further study of species- and development-stage chronic toxicity, of environmental glyphosate levels, and ongoing analysis of data relevant to determining what if any role glyphosate might be playing in worldwide amphibian decline, and suggest including amphibians in standardized test batteries.[124]

Glyphosate-based formulations can cause oxidative stress in bullfrog tadpoles and Pacific oysters.[125]

In reproductive toxicity studies performed in rats and rabbits, no adverse maternal or offspring effects were seen at doses below 175–293 mg/kg of body weight per day.[7]

Monsanto and other companies produce glyphosate products with alternative surfactants specifically formulated for aquatic use, for example the Monsanto products "Biactive" and "AquaMaster".[126][127] In 2001, the Monsanto product Vision® was studied in a forest wetlands site in Canada. Substantial mortality occurred only at concentrations exceeding the expected environmental concentrations as calculated by Canadian regulatory authorities. While it was found that site factors such as pH and suspended sediments substantially affected the toxicity in the amphibian larvae tested, overall, "results suggest that the silvicultural use of Vision herbicide in accordance with the product label and standard Canadian environmental regulations should have negligible adverse effects on sensitive larval life stages of native amphibians."[128]


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